WO2012124666A1 - Transistor à couches minces et son procédé de fabrication - Google Patents

Transistor à couches minces et son procédé de fabrication Download PDF

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Publication number
WO2012124666A1
WO2012124666A1 PCT/JP2012/056317 JP2012056317W WO2012124666A1 WO 2012124666 A1 WO2012124666 A1 WO 2012124666A1 JP 2012056317 W JP2012056317 W JP 2012056317W WO 2012124666 A1 WO2012124666 A1 WO 2012124666A1
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organic semiconductor
film
thin film
semiconductor film
film transistor
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PCT/JP2012/056317
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English (en)
Japanese (ja)
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串田　尚
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帝人株式会社
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/464—Lateral top-gate IGFETs comprising only a single gate
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate

Definitions

  • the present invention relates to a novel thin film transistor, a method for manufacturing the same, and an electric circuit having such a thin film transistor.
  • TFTs thin film transistors
  • solar cells solar cells
  • CVD chemical vapor deposition
  • sputtering is used at the time of manufacture.
  • RF-ID Radio Frequency IDentification
  • an organic semiconductor film made of an organic semiconductor material has been proposed to use.
  • a vacuum deposition apparatus and a coating apparatus used for manufacturing an organic semiconductor film are less expensive than a CVD apparatus and a sputtering apparatus used for manufacturing an inorganic semiconductor film.
  • the organic semiconductor film since the process temperature is low, the organic semiconductor film can be formed on a polymer film, paper, or the like.
  • a solution method for example, a casting method, a spin coating method, a contact printing method, or the like, in which a solution containing an organic semiconductor material is applied to a substrate, a stamp, and the like, and the solvent is removed.
  • a printing method, a dip method, and the like a vapor deposition method in which an organic semiconductor material is vapor-deposited on a substrate are known.
  • the solution method is generally known to be preferable with respect to production cost, production rate, and the like, and therefore various studies have been made.
  • stably obtaining a high-quality organic semiconductor film by a solution method has not always been sufficiently achieved.
  • Patent Document 1 and Non-Patent Documents 1 and 2 an alignment film such as a polymer layer subjected to rubbing (rubbing) is formed on a substrate, and an organic semiconductor film is formed on the alignment film. And, it is proposed to raise the temperature of the organic semiconductor film to the liquid crystal transition temperature and align the organic semiconductor film by the action of the alignment film, thereby forming an organic semiconductor film having uniaxial anisotropy in the plane. . That is, these documents propose forming an organic semiconductor film on an alignment film for aligning an organic semiconductor material in a plane direction.
  • Patent Document 2 an organic semiconductor layer having uniaxial anisotropy is formed by forming a film of an organic semiconductor material in a solution state or a molten state while applying strong shear. Has proposed.
  • Patent Document 3 an alignment film for aligning the organic semiconductor material in a direction perpendicular to the base material is formed on the base material, and the organic semiconductor film is formed on the alignment film from a releasable substrate such as a stamp. It has been proposed to transfer at the liquid crystal phase temperature and align the organic semiconductor film in the direction perpendicular to the substrate by the action of the alignment film. That is, this document proposes to improve the mobility in the in-plane direction of the organic semiconductor film by orienting the organic semiconductor material in a direction perpendicular to the base material.
  • An object of the present invention is to provide a novel thin film transistor and a manufacturing method thereof, and an electric circuit having such a thin film transistor.
  • the inventors of the present invention have a conformation in which the surface formed by the aromatic ring constituting the organic semiconductor material stands substantially perpendicular to the substrate, and the organic semiconductor material is oriented in the plane of the organic semiconductor film.
  • the present inventors have found that an organic semiconductor film can be formed by a specific method, and have devised the following thin film transistor, a manufacturing method thereof, and an electric circuit.
  • ⁇ 1> It has a source electrode, a drain electrode, a gate electrode, a gate insulating film, and an organic semiconductor film, and the source electrode and the drain electrode are insulated from the gate electrode by the gate insulating film and applied to the gate electrode.
  • the organic semiconductor film is made of an organic semiconductor material having an aromatic ring, The surface formed by the aromatic ring constituting the organic semiconductor material has a conformation that is substantially perpendicular to the substrate, and the molecular axis that maximizes the mobility of the organic semiconductor material is the organic semiconductor film In the plane, oriented in the direction of the electric field between the source electrode and the drain electrode, Thin film transistor.
  • ⁇ 2> Item ⁇ 1> above, wherein the direction of the molecular axis of the main chain of the organic semiconductor material is within ⁇ 60 ° of the direction of the electric field between the source electrode and the drain electrode in the plane of the organic semiconductor film.
  • a thin film transistor according to 1. ⁇ 3> The thin film transistor according to ⁇ 1> or ⁇ 2>, wherein the thin film transistor is not in contact with an alignment film that aligns the organic semiconductor material in a plane direction.
  • ⁇ 7> The thin film transistor according to any one of ⁇ 1> to ⁇ 6>, wherein the value of the charge mobility ratio is 5 or more.
  • ⁇ 8> Any one of ⁇ 1> to ⁇ 7> above, wherein the charge mobility in the direction in which the charge mobility of the organic semiconductor film is maximum is 0.01 cm 2 / (V ⁇ s) or more.
  • ⁇ 9> The thin film transistor according to any one of ⁇ 1> to ⁇ 8>, wherein the organic semiconductor film is in contact with a substrate or film having a contact angle with water of 50 degrees or more.
  • An electric circuit having 100 or more thin film transistors At least 80% of the thin film transistors are the thin film transistors according to any one of ⁇ 1> to ⁇ 9> above, electric circuit.
  • ⁇ 11> providing an organic semiconductor solution in which the organic semiconductor material is dissolved and / or dispersed; Applying the organic semiconductor solution onto the stamp and drying to obtain an organic semiconductor film on the stamp;
  • the thin film transistor according to any one of ⁇ 1> to ⁇ 9> above, wherein the organic semiconductor film is produced by a method including a step of transferring the organic semiconductor layer at a temperature at which the organic semiconductor material becomes liquid crystal. Production method.
  • ⁇ 12> The method according to ⁇ 11>, wherein the transferring step is performed using a roll having the stamp on the printing surface.
  • ⁇ 13> providing an organic semiconductor film made of an organic semiconductor material having an aromatic ring on a substrate or film; Applying a stress from the outside to the organic semiconductor layer at a temperature at which the organic semiconductor material becomes liquid crystal, and orienting the organic semiconductor material in a plane of the organic semiconductor film;
  • the thin film transistor of the present invention can function at a relatively high speed. Moreover, according to the method of the present invention for producing an organic semiconductor film, the organic semiconductor film used in the thin film transistor of the present invention can be produced.
  • FIG. 1 is a diagram for conceptually explaining an organic semiconductor film used in the present invention.
  • FIG. 2 is a diagram for conceptually explaining a conventional organic semiconductor film.
  • FIG. 3 is a diagram for conceptually explaining the organic semiconductor film used in the present invention.
  • FIG. 4 is a diagram illustrating a thin film transistor of the present invention.
  • FIG. 5 is a diagram showing the results of in-plane X-ray diffraction (XRD) analysis of the organic semiconductor film obtained in Example 1.
  • FIG. 6 is a diagram showing the results of in-plane X-ray diffraction (XRD) analysis of the organic semiconductor film obtained in Example 3.
  • FIG. 7 is a diagram for conceptually explaining the method of the present invention for producing an organic semiconductor film.
  • FIG. 8 is a diagram showing the direction dependency of mobility for the organic semiconductor films of Examples 1A and 8A.
  • the thin film transistor of the present invention includes a source electrode, a drain electrode, a gate electrode, a gate insulating film, and an organic semiconductor film, the source electrode and the drain electrode are insulated from the gate electrode by the gate insulating film, and the gate electrode The current flowing through the organic semiconductor film from the source electrode to the drain electrode is controlled by the voltage applied to.
  • the molecular axis that maximizes the mobility of the organic semiconductor material is the channel length direction of the organic semiconductor element, that is, the electric field between the source electrode and the drain electrode in the plane of the organic semiconductor film. Oriented in the direction. Specifically, for example, in this organic semiconductor film, the direction of the molecular axis of the main chain of the organic semiconductor material is within ⁇ 60 ° of the direction of the electric field between the source electrode and the drain electrode in the plane of the organic semiconductor film. , Within ⁇ 45 °, within ⁇ 30 °, within ⁇ 20 °, or within ⁇ 10 °.
  • the organic semiconductor film may not be in contact with the alignment film that aligns the organic semiconductor material in the plane direction.
  • such an alignment film may not be provided directly below.
  • the surface (2) formed by the aromatic ring constituting the organic semiconductor material (1) is substantially perpendicular to the substrate (10).
  • the organic semiconductor material (1) is oriented in the plane of the organic semiconductor film.
  • the fact that the surface (2) is a conformation standing substantially perpendicular to the substrate (10) and being uniaxially oriented is, for example, in in-plane X-ray diffraction (XRD) analysis. This can be confirmed by observing only the peaks due to the spacing between the surfaces.
  • XRD in-plane X-ray diffraction
  • Patent Document 2 when an organic semiconductor material in a solution state or a molten state is formed while applying strong shearing, an organic film is used without using an alignment film.
  • the orientation of the semiconductor material can be achieved, as shown in FIG. 2, the surface (2 ′) formed by the aromatic ring (1) constituting the organic semiconductor material is substantially parallel to the substrate (10). It is known that the film is oriented so as to have a stacked structure (Non-patent Document 5).
  • this surface (2 ′) is a layered structure substantially parallel to the substrate (10) is, for example, in the out-of-plane X-ray diffraction (XRD) analysis, this surface ( 2 ′) diffraction peaks are confirmed, and in the in-plane X-ray diffraction (XRD) analysis, a plurality of lamellar peaks due to the crystallization direction along the alkyl side chain (C 12 H 25 ) This can be confirmed by observation.
  • XRD out-of-plane X-ray diffraction
  • the surface (2) formed by the aromatic ring constituting the organic semiconductor material (1) has a conformation (edge-on-conformation (FIG. 1)) in which the surface (2) stands substantially perpendicular to the substrate (10).
  • the molecular axis direction of the main chain of the organic semiconductor material is uniaxially oriented in the direction of the electric field between the source electrode and the drain electrode in the plane of the organic semiconductor film.
  • a large charge mobility can be achieved in the direction of this electric field.
  • an unoriented organic semiconductor film has a large variation in the orientation direction of the organic semiconductor material, which causes a problem that characteristic variations of thin film transistors using such an organic semiconductor film are likely to occur.
  • the organic semiconductor film used in the present invention is uniaxially oriented, such variation in characteristics is reduced.
  • the surface formed by the aromatic ring constituting the organic semiconductor material has a conformation standing substantially perpendicular to the substrate, and the molecular axis of the main chain of the organic semiconductor material Is oriented in the direction of the electric field between the source electrode and the drain electrode in the plane of the organic semiconductor film, a thin film transistor that functions at a relatively high speed can be obtained.
  • organic semiconductor film used in the present invention when the organic semiconductor film used in the present invention is not in contact with an alignment film that aligns the organic semiconductor material in the plane direction, such an alignment film may have an undesirable effect on the organic semiconductor film, for example, alignment.
  • an alignment film When a defect occurs in the film and / or when the alignment film deteriorates, it is possible to avoid a decrease in the characteristics of the organic semiconductor film.
  • polyimide which is mainly used for the alignment film for aligning the organic semiconductor material in the plane direction, has a relatively high surface energy, so that the organic semiconductor film in contact therewith is disadvantageous in terms of electrical characteristics, and the organic semiconductor aromatic ring is a substrate.
  • the organic semiconductor film of the present invention that is not in contact with the alignment film, such a problem can be avoided.
  • the organic semiconductor film used in the thin film transistor of the present invention can be manufactured by the method of the present invention for manufacturing an organic semiconductor film.
  • the maximum value of the ratio of the charge mobility in any two directions in the plane ⁇ (charge mobility in the direction in which the charge mobility is maximum) / (charge mobility in the direction in which the charge mobility is minimum) ⁇ May be greater than 1.5. That is, for example, as shown in FIG. 3, in the organic semiconductor film (20) of the present invention disposed on the substrate (10), the charge mobility in the direction (arrow 22) in which the charge mobility is maximum. However, it may be larger than 1.5 times the charge mobility in the direction (arrow 24) in which the charge mobility is minimum.
  • the ratio value or maximum value of the charge mobility is, for example, 2 or more, 10 or more, 20 or more, and may be 50 or less, 30 or less, 20 or less, or 15 or less.
  • the charge mobility in the direction in which the mobility is maximum is, for example, 0.01 cm 2 / (V ⁇ s) or more, 0.05 cm 2 / (V ⁇ s) or more, or 0 It may be 10 cm 2 / (V ⁇ s) or more.
  • the charge mobility ⁇ cm 2 / (V ⁇ s) ⁇ is the charge mobility on the surface of the organic semiconductor film, and represents the ease of movement of charges that are holes or electrons. .
  • the organic semiconductor film used in the present invention can have an arbitrary thickness, for example, a thickness of 1 nm to 1 ⁇ m, or 10 nm to 500 nm.
  • Organic semiconductor material constituting the organic semiconductor film used in the present invention is an arbitrary organic semiconductor having an aromatic ring, and particularly an organic semiconductor material that can be in a liquid crystal state.
  • organic semiconductor materials include low molecular organic semiconductor molecules such as pentacene, thiophene, perylene, and fullerene materials, polyalkylthiophene, polyphenylene vinylene, polyfluorene-thiophene copolymers, and the like. Mention may be made of molecular organic semiconductor molecules.
  • the temperature at which the organic semiconductor material can be in a liquid crystal state is exemplified below:
  • the organic semiconductor film used in the present invention can be produced by any method. It may be preferable in terms of productivity to manufacture the organic semiconductor film by a solution method, that is, a printing method such as a casting method, a spin coating method, or a contact printing method, or a dipping method.
  • a solution method that is, a printing method such as a casting method, a spin coating method, or a contact printing method, or a dipping method.
  • the organic semiconductor film of the present invention is a film obtained by a solution method, it is distinguished from those produced by other methods by the presence of a trace amount of solvent remaining in the organic semiconductor film, the shape and physical properties of the film, etc. be able to.
  • the organic semiconductor film of the present invention can be produced, for example, by the method of the present invention for producing an organic semiconductor film.
  • layers other than the organic semiconductor film of the thin film transistor of the present invention may be made of an inorganic material or an organic material.
  • the electric circuit of the present invention has 100 or more, 1,000 or more, 10,000 or more, or 100,000 or more thin film transistors, and at least 80%, at least 90%, at least of these thin film transistors. 95% is the thin film transistor of the present invention.
  • a first inventive method for producing an organic semiconductor film comprises providing an organic semiconductor solution in which an organic semiconductor material is dissolved and / or dispersed, applying the organic semiconductor solution onto a stamp and drying, Obtaining an organic semiconductor film on the stamp, and transferring the organic semiconductor layer at a temperature at which the organic semiconductor material becomes liquid crystal.
  • the organic semiconductor layer is transferred at a temperature at which the organic semiconductor material becomes liquid crystal, thereby enabling transfer by the stamp and the base material.
  • the surface formed by the aromatic ring constituting the organic semiconductor material can be aligned in a conformation that is substantially perpendicular to the substrate Become.
  • the aromatic ring of the organic semiconductor material is self-organized in a conformation that is substantially perpendicular to the stamp at the air side interface. This is presumably because air is theoretically superhydrophobic and therefore has little influence on the organic semiconductor, whereby the organic semiconductor material itself takes the most stable conformation at least on the air side of the organic semiconductor film.
  • the aligned organic semiconductor film (210) in the liquid crystal state is transferred from the stamp (220) to the base material (250) using a roller (230), for example, 220) and the substrate (250) are subjected to stress, particularly shear stress, on the organic semiconductor film (210).
  • the aromatic ring of the organic semiconductor material of the organic semiconductor film (210) maintains a conformation that is preliminarily standing substantially perpendicular to the stamp.
  • it is considered to be oriented with respect to the rotation direction (261) of the roller indicated by the arrow (231) or the vertical direction (262) thereof.
  • the transfer temperature within the liquid crystal phase temperature range of the organic semiconductor film, the organic semiconductor film becomes a liquid crystal phase, and molecular orientation is facilitated even with a slight shear stress.
  • the organic semiconductor layer can be transferred from the stamp to a substrate or film.
  • a substrate or film may be any substrate or film that is intended to have an organic semiconductor film disposed thereon.
  • examples of such a substrate include an inorganic material such as a silicon wafer and glass, and an organic material such as a polymer film.
  • this substrate or film may have a contact angle with water of 50 degrees or more, 60 degrees or more, 70 degrees or more, 80 degrees or more, 90 degrees or more, or 100 degrees or more. That is, this substrate or film may be a substrate or film having a low surface energy.
  • the organic semiconductor film is transferred to the substrate or film having a low surface energy by the method of the present invention, the surface formed by the aromatic ring constituting the organic semiconductor material is substantially perpendicular to the substrate. It becomes easy to take formation.
  • the stamp to which the organic semiconductor solution is applied in the method of the present invention has a surface having a relatively large contact angle with water, that is, for example, a contact angle with water of 40 ° or more, 50 ° or more, 60 ° or more, 70 ° or more, 80 You may have the surface which is (degree) or more, 90 degree or more, 100 degree or more, or 105 degree or more.
  • a relatively large contact angle of the surface of the substrate with water means that the surface is relatively lyophobic, that is, the surface energy of the surface is relatively small.
  • the adhesion between the obtained organic semiconductor film and the transfer portion is relatively weak, and therefore, a relatively lyophobic substrate.
  • the organic semiconductor film can be transferred onto the surface of the material, that is, the surface of the substrate having a contact angle with water of 50 ° or more, for example.
  • the transfer part of a general contact print stamp is generally a lyophilic solution in order to improve the wettability with respect to the organic semiconductor solution thereon, thereby enabling the stable formation of a film of the organic semiconductor solution.
  • a transfer portion of a conventional contact print stamp the adhesion between the obtained organic semiconductor film and the transfer portion is relatively strong, and therefore relatively lyophobic. It has been difficult to transfer the organic semiconductor film onto the surface of the substrate, that is, the surface of the substrate having a contact angle with water of 50 ° or more, for example.
  • a stamp having a surface with a relatively large contact angle with water can be obtained, for example, by treating the surface of the stamp with a lyophobic material.
  • lyophobic materials include silane, silazane, fluorine compounds, polyimide, polyester, polyethylene, polyphenylene sulfide, polyparaxylene, polyethylene terephthalate, polyethylene naphthalate, polydimethylsiloxane, and combinations thereof. it can.
  • any method such as a casting method, a spin coating method, or a dipping method can be used.
  • the organic semiconductor solution applied on the stamp is dried to obtain the organic semiconductor film on the stamp.
  • this drying can be performed, for example, by exposing the organic semiconductor solution on the stamp to an atmosphere of more than 40 ° C., 50 ° C., 70 ° C. or 100 ° C. This drying can also be performed by removing the solvent from the organic semiconductor solution under reduced pressure.
  • the organic semiconductor film on the stamp can be directly transferred onto a substrate such as a silicon wafer or a polymer film. Also, the organic semiconductor film on the stamp can be transferred to another stamp and transferred from the other stamp to the substrate.
  • the transfer of the organic semiconductor film from the first stamp to the base material or another stamp can be achieved by bringing the stamp holding the organic semiconductor film into contact with the base material or another stamp.
  • the transfer conditions such as the contact time, the stamp, and the temperature of the base material can be arbitrarily determined so that the organic semiconductor material becomes liquid crystal and can be transferred.
  • this transfer can be performed such that the temperature of the base material or other stamp is higher than the temperature of the stamp.
  • This transfer also treats the surface of the stamp to reduce adhesion to the organic semiconductor film and / or treats the surface of the substrate or other stamp to increase adhesion to the organic semiconductor film. Can be achieved. Still further, this transfer can be achieved by a combination of the above.
  • the other stamp used in the method of the present invention is an arbitrary stamp that can transfer an organic semiconductor film formed on the stamp, and from which the organic semiconductor film can be transferred to a substrate, That is, it may be a contact print stamp.
  • Such other stamps can be made of, for example, polysiloxane.
  • the transfer of the organic semiconductor film from another stamp to the base material can be performed as described for the transfer of the organic semiconductor film from the stamp to the base material or another stamp.
  • the method of the second present invention for producing an organic semiconductor film includes a step of providing an organic semiconductor film made of an organic semiconductor material having an aromatic ring on a substrate or film, and a temperature at which the organic semiconductor material is liquid crystallized. Applying an external stress to the layer to orient the organic semiconductor material in the plane of the organic semiconductor film.
  • the provision of the organic semiconductor film on the substrate or film can be performed by any method, for example, a casting method, a spin coating method, a printing method such as a contact printing method, a solution method such as a dipping method, and the like. It can be provided using a vapor deposition method in which an organic semiconductor material is vapor-deposited on a substrate.
  • an external stress is applied to the organic semiconductor layer at a temperature at which the organic semiconductor material becomes liquid crystal, particularly a shear stress, for example, the stamp is pressed against the base material
  • a shear stress for example, the stamp is pressed against the base material
  • the organic semiconductor film of the present invention can be produced.
  • BGTC type bottom gate / top contact type
  • Water contact angle The water contact angle was measured with pure water at 25 ° C. using a water contact angle meter CA-X manufactured by Kyowa Interface Science.
  • Charge mobility The charge mobility of the organic semiconductor film was evaluated using a 4200-SCS type semiconductor evaluation apparatus manufactured by Keithley. The standard deviation of charge mobility was calculated by evaluating the characteristics of 10 or more elements.
  • Example 1 (Production of stamps for contact printing) A silicone rubber (SIM-260 manufactured by Shin-Etsu Chemical Co., Ltd.) was cured into a flat plate shape, and oligomers were removed using hexane as a stamp material.
  • the stamp material is cut into 20 mm square, a mask corresponding to the transfer portion is placed on the stamp material, the transfer portion is masked, and the stamp material in which the transfer portion is thus masked is subjected to UV (ultraviolet) -ozone treatment. Performed for 30 minutes. That is, the transfer portion was not subjected to UV-ozone treatment, and the peripheral portion was subjected to UV-ozone treatment. This UV-ozone treatment provided a lyophilic surface at the periphery.
  • the water contact angle of the transfer part not subjected to UV-ozone treatment was 110 °, and the water contact angle of the peripheral part subjected to UV-ozone treatment for 30 minutes was 44 °. Further, twelve transfer portions exist on the stamp, and the size of each transfer portion was 100 ⁇ m ⁇ 2 mm.
  • PQT Poly [bis (3-dodecyl-2-thienyl) -2,2′-dithiophene-5,5′-diyl]
  • a mass part was dissolved by heating in 99.5 parts by mass of toluene to obtain a PQT solution as an organic semiconductor solution.
  • This PQT solution was spin coated (1800 rpm, 20 seconds) onto the patterned stamp material. Thereafter, the PQT solution was aged and dried for about 10 minutes as it was, thereby forming an organic semiconductor film on the stamp.
  • n-type silicon wafer with a 300 nm thermal oxide film (plane orientation ⁇ 100>, specific resistance 0.05 ⁇ ) was treated with hot concentrated sulfuric acid for 30 minutes, and then several times using pure water, acetone, toluene, and hexane. Ultrasonic cleaning was performed twice. Further, after cleaning for 30 minutes with a UV ozone cleaning device, surface treatment was performed with octadecyltrichlorosilane (OTS). In addition, the process of the base material by OTS was performed as follows.
  • a 20 mM toluene solution of OTS was prepared.
  • the above silicon substrate was immersed in the obtained OTS solution and held for 7 days. After soaking, the substrate was washed with toluene and ethanol and ultrasonically washed in ethanol for 30 minutes. All the steps so far were performed in a glove box in which the humidity was controlled to 3% or less. Thereafter, the substrate was washed with pure water and heat-treated at 100 ° C. for 5 minutes to obtain an OTS-treated substrate.
  • the stamp which has an organic-semiconductor film was fixed to the roller, and the roller with a stamp was obtained.
  • the silicon substrate was heated and held at 135 ° C., the above-mentioned stamped roller was brought into contact therewith, and rotated to transfer the entire organic semiconductor film to the substrate.
  • Example 1A In the same manner as in Example 1, a PQT film was formed, and a source electrode and a drain electrode were formed to obtain a thin film transistor.
  • the moving direction of the roller (the direction in which the mobility is maximum, that is, the direction of the molecular axis of the main chain of the organic semiconductor material) and the direction of the electric field between the source electrode and the drain electrode The angle between them was set to 0 °, 15 °, 30 °, 45 °, 60 °, 75 °, and 90 °.
  • Example 2 The same procedure as in Example 2 was performed except that the transfer temperature was 140 ° C. The evaluation results are shown in Table 2.
  • Example 3 The same procedure as in Example 1 was performed except that the transfer temperature was 130 ° C.
  • the evaluation results are shown in Table 2.
  • FIG. 6 shows the result of in-plane X-ray diffraction measurement of the transfer film in the direction parallel to and perpendicular to the transfer direction.
  • a peak in the (010) direction is observed, but the X-ray diffraction intensity is clearly different between the parallel direction A and the vertical direction B, indicating that the PQT film is uniaxially oriented.
  • FIG. 6 only the (010) peak is observed, and it is clear that the thiophene ring has a conformation that stands perpendicular to the substrate.
  • Example 5 (Comparison) In the same manner as in Example 1, a PQT thin film was formed on the stamp. Same as Example 1 except that the solvent was dried by allowing it to stand for 10 minutes, and then the PQT thin film was heat-treated at 130 ° C. for 10 minutes under reduced pressure and transferred to the substrate at a transfer temperature of 80 ° C. Implemented. The evaluation results are shown in Table 2.
  • Example 6 (Comparison) The same procedure as in Example 1 was performed except that the transfer temperature was 80 ° C. The evaluation results are shown in Table 2.
  • Example 7 (Comparison) The device fabricated in Example 6 was heat-treated at 135 ° C. for 5 minutes under vacuum. The evaluation results are shown in Table 2.
  • Example 8 (Comparison) The same procedure as in Example 7 was performed, except that a PQT film was directly formed on the substrate by spin coating using a 0.5% toluene solution of PQT. The evaluation results are shown in Table 2.
  • Example 8A (comparison) >> In the same manner as in Example 8, a PQT film was formed, and a source electrode and a drain electrode were formed to obtain a thin film transistor.
  • the moving direction of the roller (the direction in which the mobility is maximum, that is, the direction of the molecular axis of the main chain of the organic semiconductor material) and the direction of the electric field between the source electrode and the drain electrode The angle between them was set to 0 °, 15 °, 30 °, 45 °, 60 °, 75 °, and 90 °.
  • Example 9 (Comparison) A device was fabricated in the same manner as in Example 1 except that polyhexylthiophene (P3HT: Poly (3-HexylThiophene)) (Plexcores Inc. Plexcore OS1100) was used as the organic semiconductor. Thereafter, heat treatment was performed at 100 ° C. for 30 minutes under vacuum, and the characteristics were measured. The evaluation results are shown in Table 2.
  • P3HT Poly (3-HexylThiophene)
  • Plexcore OS1100 Plexcore OS1100
  • Example 10 Poly [(9,9-dioctylfluorenyl-2,7-diyl) -co-bithiophene] (“F8T2”) (ADS2008P molecular weight 43000, dispersion 2.8, manufactured by American Dye Source) was used as an organic semiconductor, and was transferred. The same operation as in Example 1 was conducted except that the temperature was 280 ° C. The evaluation results are shown in Table 2.
  • Example 12 (Comparison) The same procedure as in Example 10 was performed except that a F8T2 0.5% toluene solution was used to directly form an F8T2 film on the substrate by spin coating. The evaluation results are shown in Table 2.
  • Example 12A (Comparison)
  • F8T2 poly [(9,9-dioctylfluorenyl-2,7-diyl) -co-bithiophene]
  • a thin film transistor was prepared in accordance with Non-Patent Document 7, except that the transfer temperature was 280 ° C., that is, an organic semiconductor layer was formed while applying strong shearing. The evaluation results are shown in Table 2.
  • Example 13 Except that poly (2,5-bis (3-tetradecylthiophen-2-yl) thieno [3,2, b] thiophene) (“pBTTT-C14”) was used as the organic semiconductor and the transfer temperature was 150 ° C. The same procedure as in Example 1 was performed. The evaluation results are shown in Table 2.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Thin Film Transistor (AREA)

Abstract

La présente invention concerne un nouveau transistor à couches minces, son procédé de fabrication et un circuit électrique doté d'un tel transistor à couches minces. Ledit transistor à couches minces comprend une électrode source, une électrode drain, une électrode de grille, un isolant de graille, et un film semi-conducteur organique. L'électrode source et l'électrode drain sont isolées de l'électrode de grille par l'isolant de grille et le courant électrique qui circule de l'électrode source à l'électrode drain à travers le film semi-conducteur est contrôlé par la tension appliquée à l'électrode de grille. Ledit film semi-conducteur organique est constitué d'un matériau semi-conducteur organique (1) comprenant un noyau aromatique, et il présente une conformation dans laquelle une surface (2) formée par le noyau aromatique constituant le matériau semi-conducteur organique est sensiblement perpendiculaire à un substrat (10). L'axe moléculaire sur lequel la mobilité du matériau semi-conducteur organique (1) est maximale est orienté dans le sens du champ électrique entre l'électrode source et l'électrode drain dans le plan du film semi-conducteur.
PCT/JP2012/056317 2011-03-14 2012-03-12 Transistor à couches minces et son procédé de fabrication WO2012124666A1 (fr)

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JP2014146665A (ja) * 2013-01-28 2014-08-14 Sijtechnology Inc 有機半導体膜の製造方法、その製造装置および有機半導体基板
CN113540352A (zh) * 2021-06-18 2021-10-22 吉林大学 溶液加工与真空蒸镀结合制备有机晶体薄膜的方法

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WO2005045939A1 (fr) * 2003-11-11 2005-05-19 Matsushita Electric Industrial Co., Ltd. Transistor en couches minces et procede de fabrication
JP2008300480A (ja) * 2007-05-30 2008-12-11 Konica Minolta Holdings Inc 有機薄膜トランジスタ、有機薄膜トランジスタシート及び有機薄膜トランジスタの製造方法
JP2009200479A (ja) * 2008-01-22 2009-09-03 Dainippon Printing Co Ltd 有機半導体素子の製造方法
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JP2009215557A (ja) * 2002-10-30 2009-09-24 Sumitomo Chemical Co Ltd 高分子化合物およびそれを用いた高分子発光素子
WO2005045939A1 (fr) * 2003-11-11 2005-05-19 Matsushita Electric Industrial Co., Ltd. Transistor en couches minces et procede de fabrication
JP2008300480A (ja) * 2007-05-30 2008-12-11 Konica Minolta Holdings Inc 有機薄膜トランジスタ、有機薄膜トランジスタシート及び有機薄膜トランジスタの製造方法
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NOBUTAKA TANIGAKI: "Fabrication of Oriented Thin Films of Opto-Electronic Functional Polymers by Friction Transfer Method: Oriented Thin Films of Polythiophenes and Polyanilines", TECHNICAL REPORT OF IEICE, vol. 108, no. 483, 6 March 2009 (2009-03-06), pages 7 - 10 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014146665A (ja) * 2013-01-28 2014-08-14 Sijtechnology Inc 有機半導体膜の製造方法、その製造装置および有機半導体基板
CN113540352A (zh) * 2021-06-18 2021-10-22 吉林大学 溶液加工与真空蒸镀结合制备有机晶体薄膜的方法

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